Yarns and fabrics having a wash-durable non-electrically conductive topically applied metal-based finish

ABSTRACT

Durable non-electrically conductive metal treatments (such as coatings or finishes) for yarns and textile fabrics. Such treatments preferably comprise silver and/or silver ions; however, other metals, such as zinc, iron, copper, nickel, cobalt, aluminum, gold, manganese, magnesium, and the like, may also be present or alternatively utilized. Such a treatment provides, as one example, an antimicrobial fiber and/or textile fabric which remains on the surface and does not permit electrical conductivity over the surface. The treatment is extremely durable on such substrates; after a substantial number of standard launderings and dryings, the treatment does not wear away in any appreciable amount and thus the substrate retains its antimicrobial activity (or other property). The method of adherence to the target yarn and/or fabric may be performed any number of ways, most preferably through the utilization of a binder system or through a transfer method from a donor fabric to a target textile fabric in the presence of moisture and upon exposure to heat. The particular methods of adherence, as well as the treated textile fabrics and individual fibers are also encompassed within this invention.

FIELD OF THE INVENTION

This invention relates to improvements in durable non-conductivemetal-based treatments (such as coatings or finishes) for yarns andtextile fabrics. Such treatments preferably comprise silver and/orsilver ions; however, other metals, such as zinc, iron, copper, nickel,cobalt, aluminum, gold, manganese, magnesium, and the like, may also bepresent or alternatively utilized. Such a treatment provides, as oneexample, an antimicrobial fiber and/or textile fabric which remains onthe surface and does not permit electrical conductivity over thesurface. The treatment is extremely durable on such substrates; after asubstantial number of standard launderings and dryings, the treatmentdoes not wear away in any appreciable amount and thus the substrateretains its antimicrobial activity (or other property). The method ofadherence to the target yarn and/or fabric may be performed any numberof ways, most preferably through the utilization of a binder system orthrough a transfer method from a donor fabric to a target textile fabricin the presence of moisture and upon exposure to heat. The particularmethods of adherence, as well as the treated textile fabrics andindividual fibers are also encompassed within this invention.

DISCUSSION OF THE PRIOR ART

There has been a great deal of attention in recent years given to thehazards of bacterial contamination from potential everyday exposure.Noteworthy examples of such concern include the fatal consequences offood poisoning due to certain strains of Eschericia coli being foundwithin undercooked beef in fast food restaurants; Salmonellacontamination causing sicknesses from undercooked and unwashed poultryfood products; and illnesses and skin infections attributed toStaphylococcus aureus, Klebsiella pneumoniae, yeast, and otherunicellular organisms. With such an increased consumer interest in thisarea, manufacturers have begun introducing antimicrobial agents withinvarious household products and articles. For instance, certain brands ofpolypropylene cutting boards, liquid soaps, etc., all containantimicrobial compounds. The most popular antimicrobial for sucharticles is triclosan. Although the incorporation of such a compoundwithin liquid or polymeric media has been relatively simple, othersubstrates, including the surfaces of textiles and fibers, have provenless accessible. There is a long-felt need to provide effective,durable, and long-lasting antimicrobial characteristics for textilesurfaces, in particular on apparel fabrics, and on film surfaces. Suchproposed applications have been extremely difficult to accomplish withtriclosan, particularly when wash durability is a necessity (triclosaneasily washes off any such surfaces). Furthermore, although triclosanhas proven effective as an antimicrobial compound, the presence ofchlorines and chlorides within such a compound causes skin irritationwhich makes the utilization of such with fibers, films, and textilefabrics for apparel uses highly undesirable. Furthermore, there arecommercially available textile products comprising acrylic and/oracetate fibers co-extruded with triclosan (for example Celanese marketssuch acetate fabrics under the name Microsafe™ and Acordis markets suchacrylic fibers under the tradename Amicor™). However, such anapplication is limited to those types of fibers; it does not workspecifically for and within polyester, polyamide, cotton, spandex, etc.,fabrics. Furthermore, this co-extrusion procedure is very expensive.

Silver-containing inorganic microbiocides have recently been developedand utilized as antimicrobial agents on and within a plethora ofdifferent substrates and surfaces. In particular, such microbiocideshave been adapted for incorporation within melt spun synthetic fibers,as taught within Japanese unexamined Patent Application No. H11-124729,in order to provide certain fabrics which selectively and inherentlyexhibit antimicrobial characteristics. Furthermore, attempts have beenmade to apply such specific microbiocides on the surfaces of fabrics andyams with little success from a durability standpoint. A topicaltreatment with such compounds has never been successfully applied as adurable finish or coating on a fabric or yam substrate. Although suchsilver-based agents provide excellent, durable, antimicrobialproperties, to date such is the sole manner available within the priorart of providing a long-lasting, wash-resistant, silver-basedantimicrobial textile. However, such melt spun fibers are expensive tomake due to the large amount of silver-based compound required toprovide sufficient antimicrobial activity in relation to the migratorycharacteristics of such a compound within the fiber itself to itssurface. A topical coating is also desirable for textile and filmapplications, particularly after finishing of the target fabric or film.Such a topical procedure permits treatment of a fabric's individualfibers prior to or after weaving, knitting, and the like, in order toprovide greater versatility to the target yam without altering itsphysical characteristics. Such a coating, however, must prove to be washdurable, particularly for apparel fabrics, in order to be functionallyacceptable. Furthermore, in order to avoid certain problems, it ishighly desirable for such a metallized treatment to be electricallynon-conductive on the target fabric, yarn, and/or film surface. With thepresence of metals and metal ions, such a wash durable, non-electricallyconductive coating has not been available in the past. Such animprovement would thus provide an important advancement within thetextile, yam, and film art. Although antimicrobial activity is onedesired characteristic of the inventive metal-treated fabric, yarn, orfilm, this is not a required property of the inventive article.Odor-reduction, heat retention, distinct colorations, reduceddiscolorations, improved yam and/or fabric strength, resistance to sharpedges, etc., are all either individual or aggregate properties which maybe accorded the user of such an inventive treated yarn, fabric, or film.

DESCRIPTION OF THE INVENTION

It is thus an object of the invention to provide a simple manner ofeffectively treating a yarn, textile, or film with a wash-durableantimicrobial metal or metal-ion containing treatment. A further objectof the invention is to provide a treatment for textiles or films whichis wash-durable and continuously reduces and/or removes malodors fromthe target surface through the utilization of metals or metal-ions.Another object of the invention is to provide an aesthetically pleasingmetal- or metal-ion-treated textile or film which is non-electricallyconductive, wash durable, non-yellowing, non-irritating to skin, andwhich provides either or both antimicrobial or odor-reducing properties.

Accordingly, this invention encompasses a treated substrate comprising anon-electrically conductive treatment comprising metal-containingcompounds selected from the group consisting of metalparticle-containing compounds, metal ion-containing compounds, and anycombinations thereof, and a substrate selected from the group consistingof a yam, a fabric comprised of individual yarns, and a film; whereinsaid compound or compounds is present on at least a portion of thesurface of said substrate; and wherein at least about 30%, of theoriginally adhered metal-containing treatment remains on said treatedportion of said substrate surface after at least 10 washes, said washesbeing performed in accordance with the wash procedure as part of AATCCTest Method 130-1981. Still more preferably at least 50% of themetal-containing compounds remain after 10 washes, more preferably 60%after 10 washes, and most preferably at least 75% after the same numberof washes. Furthermore, it is also highly preferred that at least 30% ofthe finish is retained after 15 washes, 20 washes, and most preferablyabout 30 washes. Also, and alternatively, this invention encompasses atreated substrate comprising a non-electrically conductive treatmentcomprising metal-containing compounds selected from the group consistingof metal particle-containing compounds, metal ion-containing compounds,and any combinations thereof, and a substrate selected from the groupconsisting of a yarn, a fabric comprised of individual yams, and a fihn;wherein said compound or compounds is adhered to at least a portion ofthe surface of said substrate; and wherein said treated substrateexhibits a log kill rate for Staphylococcus aureus of at least 1.5,preferably above 2.0, more preferably above 3.0, and a log kill rate forKlebsiella pneumoniae of at least 1.5, preferably above 2.0, and morepreferably above 3.0, both as tested in accordance with AATCC TestMethod 100-1993 for 24 hour exposure, after at least 10 washes, saidwashes performed in accordance with the wash procedure as part of AATCCTest Method 130-1981. Such an invention also encompasses the differentmethods of producing such a treated substrate. The wash durability testnoted above is standard and, as will be well appreciated by one ofordinary skill in this art, is not intended to be a required orlimitation within this invention. Such a test method merely provides astandard which, upon 10 washes in accordance with such, the inventivetreated substrate will not lose an appreciable amount of itselectrically non-conductive metal finish.

The amount retained may be measured in any standard manner, such as, forexample, inductively coupled plasma (ICP), X-ray fluorescence (XRF), oratomic absorption (AA) spectroscopic analysis. Or, again, in thealternative, the durability of certain finishes may be determined (i.e.,the retention of finish on the surface) in relation to antimicrobialperformance. Thus, with an antimicrobially effective finish, theexhibition of log kill rates for Klebsiella pneumoniae or Staphylococcusaureus after 24 hours exposure in accordance with AATCC Test Method100-1993 of at least 1.5, and higher, as noted above, for both after 10washes in accordance with AATCC Test Method 130-1981. Preferably, theselog kill rates are above 3.2, more preferably 3.5, and most preferablyat least 4.0. Again, such log kill rates after the minimum number ofwashes symbolizes the desired durability level noted above.

Nowhere within the prior art has such a specific treated substrate ormethod of making thereof been disclosed, utilized, or fairly suggested.The closest art is a product marketed under the tradename X-STATIC®which is a fabric article electrolessly plated with a silver coating.Such a fabric is highly electrically conductive and is utilized forstatic charge dissipation. Also, the coating alternatively exists as aremovable silver powder finish on a variety of surfaces. Theaforementioned Japanese patent publication to Kuraray is limited tofibers within which a silver-based compound has been incorporatedthrough melt spun fiber techniques. Nowhere has such a wash-durabletopical treatment as now claimed been mentioned or alluded to.

Any yarn, fabric, or film may be utilized as the substrate within thisapplication. Thus, natural (cotton, wool, and the like) or syntheticfibers (polyesters, polyamides, polyolefins, and the like) mayconstitute the target substrate, either by itself or in any combinationsor mixtures of synthetics, naturals, or blends or both types. As for thesynthetic types, for instance, and without intending any limitationstherein, polyolefins, such as polyethylene, polypropylene, andpolybutylene, halogenated polymers, such as polyvinyl chloride,polyesters, such as polyethylene terephthalate, polyester/polyethers,polyamides, such as nylon 6 and nylon 6,6, polyurethanes, as well ashomopolymers, copolymers, or terpolymers in any combination of suchmonomers, and the like, may be utilized within this invention. Nylon-6,nylon-6,6, polypropylene, and polyethylene terephthalate (a polyester)are particularly preferred. Additionally, the target fabric may becoated with any number of different films, including those listed ingreater detail below. Furthermore, the substrate may be dyed or coloredto provide other aesthetic features for the end user with any type ofcolorant, such as, for example, poly(oxyalkylenated) colorants, as wellas pigments, dyes, tints, and the like. Other additives may also bepresent on and/or within the target fabric or yarn, including antistaticagents, brightening compounds, nucleating agents, antioxidants, UVstabilizers, fillers, permanent press finishes, softeners, lubricants,curing accelerators, and the like. Particularly desired as optional andsupplemental finishes to the inventive fabrics are soil release agentswhich improve the wettability and washability of the fabric. Preferredsoil release agents include those which provide hydrophilicity to thesurface of polyester. With such a modified surface, again, the fabricimparts improved comfort to a wearer by wicking moisture. The preferredsoil release agents contemplated within this invention may be found inU.S. Pat. Nos. 3,377,249; 3,540,835; 3,563,795; 3,574,620; 3,598,641;3,620,826; 3,632,420; 3,649,165; 3,650,801; 3,652,212; 3,660,010;3,676,052; 3,690,942; 3,897,206; 3,981,807; 3,625,754; 4,014,857;4,073,993; 4,090,844; 4,131,550; 4,164,392; 4,168,954; 4,207,071;4,290,765; 4,068,035; 4,427,557; and 4,937,277. These patents areaccordingly incorporated herein by reference. Additionally, otherpotential additives and/or finishes may include water repellentfluorocarbons and their derivatives, silicones, waxes, and other similarwater-proofing materials.

The particular treatment must comprise at least one type ofmetal-incorporating compound (namely metal particles), metal-ioncontaining particles, or mixtures thereof. The term metal is intended toinclude any such historically understood member of the periodic chart(including transition metals, such as, without limitation, silver, zinc,copper, nickel, iron, magnesium, manganese, vanadium, gold, cobalt,platinum, and the like, as well as other types including, withoutlimitation, aluminum, tin, calcium, magnesium, antimony, bismuth, andthe like). More preferably, the metals utilized within this inventionare generally those known as the transition metals. Of the transitionmetals, the more preferred metals are silver, zinc, gold, copper,nickel, manganese, and iron. Most preferred are silver and zinc. Suchmetals provide the best overall desired characteristics, such as,preferably, antimicrobial and/or odor reducing characteristics, certaincolorations, good lightfastness, and, most importantly, wash durabilityon the target substrate.

The term metal particle is intended to encompass any compound withinwhich the metal is present in its pure non-ionic state (thus silverparticles are present, as one example). The term metal-ion containingencompasses compounds within which the ionic species of metals arepresent (such as metal oxides, including, as mere examples, zinc oxidefor Zn²⁺, silver oxide for Ag⁺, and iron oxide for Fe²⁺ or Fe³⁺, or, asalternatives, ion-exchange resins, zeolites, or, possibly substitutedglass compounds, which release the particular metal ion bonded theretoupon the presence of other anionic species). The preferred metalparticle compound is produced through a reduction procedure and may beany of silver, nickel, copper, zinc, and iron. With a reducing agent,the salts utilized for this purpose are thus preferably silver (I)nitrate, nickel (II) perchlorate, copper (II) acetate, and iron (II)sulfate. The preferred metal-ion containing compound for this inventionis an antimicrobial silver zirconium phosphate available from Milliken &Company, under the tradename ALPHASAN®, although any silver-containingantimicrobial compound, including, for instance, and as merely someexamples, a silver-substituted zeolite available from Sinanen under thetradename ZEOMIC® AJ, or a silver-substituted glass available fromIshizuka Glass under the tradename IONPURE®, may be utilized either inaddition to or as a substitute for the preferred species. Also preferredas such a compound is zinc oxide, zinc ricinoleate, zinc chloride, andzinc sulfate. Other metals, as noted above, may also be utilized;however, from a performance standpoint, silver and zinc, are mostpreferred. Generally, such a metal compound is added in an amount offrom about 0.01 to 40% by total weight of the particular treatmentcomposition; more preferably from about 0.05 to about 30%; and mostpreferably from about 0.1 to about 3 0%, all dependent upon the selectedmethod of application. The metal compound is then added to the targetsubstrate in a) amounts of between 0.01 and 1.0 ounces per square yard,or, alternatively, b) from about 0.01 to about 5% owf, depending on theselected application and method for measuring. Such proportions providethe best antimicrobial and/or odor-reducing performance in relation towash durability, electrical non-conductivity, and overall cost.Preferably this metal compound add-on weight is a) about 0.1, or b)about 1.0% owf. The treatment itself, including any necessary binders,adherents, thickeners, and the like, is added to the substrate in anamount of a) about 0.01 to about 4.0 ounces per square yard, or b) fromabout 0.01 to about 10% owf.

Furthermore, the inventive substrates necessarily do not exhibit anyappreciable electrical conductivity (due to the low amounts of metalpresent and thus the nonexistence of any percolation over or through thetarget substrate) as measured by attaching a two-inch by two-inch fabricspecimen to two electrodes and applying a voltage gradient of about 100volts per inch through the fabric (i.e., in accordance with AATCC TestMethod 76-1978). The measured resistance in ohms per square inch shouldexceed about 10,000, preferably 1,000,000, and most preferably 1×110 inorder to provide a substantially non-electrically conductive fabric.

The selected substrate may be any of an individual yarn, a fabriccomprising individual fibers or yarns (though not necessarily previouslycoated yarns), or a film (either standing alone or as laminated to afabric, as examples). The individual fibers or yarns may be of anytypical source for utilization within fabrics, including natural fibers(cotton, wool, ramie, hemp, linen, and the like), synthetic fibers(polyolefins, polyesters, polyamides, polyaramids, acetates, rayon,acylics, and the like), and inorganic fibers (fiberglass, boron fibers,and the like). The target yarn may be of any denier, may be of multi- ormono-filament, may be false-twisted or twisted, or may incorproatemultiple denier fibers or filaments into one single yarn throughtwisting, melting, and the like. The target fabrics may be produced ofthe same types of yarns discussed above, including any blends thereof.Such fabrics may be of any standard construction, including knit, woven,or non-woven forms. The films may be produced from any thermoplastic orthermoset polymer, including, but not limited to, polyolefins(polypropylene, polyethylene, polybutylene), polyvinyl chloride,polyvinylidene chloride, polyvinyl acetate, and the like, polyesters(polyethylene terephthalate, isophthalates, and the like) polyethers,acetates, acrylics, and polyamides, as well as any copolymer films ofany of the above. Such films may be extruded, blown, rolled, and thelike, and may be produced in situ on the surface of a target fabric orproduced separately and subsequently adhered or laminated on a targetsurface. Also, such films may be produced, treated, and utilizedseparately from any other substrates.

The yarns are preferably incorporated within specific fabrics, althoughany other well known utilization of such yarns may be undertaken withthe inventive articles (such as tufting for carpets). The inventivefabrics may also be utilized in any suitable application, including,without limitation, apparel, upholstery, bedding, wiping cloths, towels,gloves, rugs, floor mats, drapery, napery, bar runners, textile bags,awnings, vehicle covers, boat covers, tents, and the like. The inventivefilms may be present on fabrics, or utilized for packaging, as coatingsfor other types of substrates, and the like.

Yarn and fabric substrates are preferably treated with a metal particleor metal-ion containing finish. Films are preferably treated withmetal-ion containing formulations on the surface of film-coated fabrics.

Metal Particle Treatments

The preferred metal particle composition will generally comprise fourcomponents: water, a metal salt, a reducing agent, and a polymericbinder. As noted above, the metal is produced through the reduction ofthe metal ion upon dissolution of the metal salt in solution. Thisspecific process actually blends two different technologies,specifically the formation of colloidal particles by chemical reductionand steric stabilization of such particles by surfactant or polymer andthe modification of a fiber (or textile) surface through the utilizationof a polymeric binder. In the instance, the steric stabilizer and thefiber (or textile) binder are the same polymeric compound.

Such a metal particle dispersion is generally produced as follows: Asolution of the polymeric binder and water is produced having a polymerconcentration between 0.1% and 20% (w/w). The solution is then dividedbetween two containers, one containing a dissolved metal salt (i.e. ametal salt MA dissociates completely to M⁺ and A⁻) and in the other, adissolved reducing agent. When the two solutions are thoroughly mixed,they are then combined very quickly. When combined, the reducing agenttransfers an electron to the metal cation and reduces it to its neutralform (M_(n) ⁺+e⁻→M_(n) ⁰). The metal atoms quickly agglomerate to formlarger (1-1000 nm) particles. The steric stabilizer acts by adsorbing tothe surface of the growing particles and thereby prevents catastrophicflocculation of the particles into macroscopic (˜mm in diameter)aggregates by limiting the distance of closest approach.

It is important to note that the selection of the particular polymericbinder is crucial to the success in attaining the desired durability andeffectiveness of the specific coating as this binder component must meeta number of important criteria. First, since high salt concentrationsare necessary to generate large numbers of metal particles, and suchsalts generally cause many polymeric binder dispersions to flocculateout of solution, the particular binder must not react in such a mannerin order to effectively stabilize the particles that are produced (asnoted above). Secondly, the binder must not act like typical textilebinders (which do not stabilize the particles and thus allow thenucleated particles to flocculate rapidly into macroscopic assemblies)which would render the resultant solution unusable in this application.Thirdly, it is important that the polymeric stabilizer, once processed,be able to withstand home washing under a wide range of conditions andmaintain the silver concentration on the textile. Thus, it must not bereadily soluble in water, must not be susceptible to attack by standardand/or industrial detergents, solvents, and/or bleaches, and must notmelt upon exposure to drying temperatures. The utilization of such aspecific binder to provide a metal coating to fibers and/or fabrics isthus drastically different from other previous practices in this areaand permits a topical application of a such a coating either before orafter the particular substrate has been finished. In order to providethe requisite wash durability, this binder must pass these stringentcriteria. No teaching or fair suggestion exists within the prior art ofsuch requirements.

As noted previously, the preferred metal salts for this procedure aresilver (I) nitrate, nickel (II) perchlorate, copper (II) acetate, andiron (II) sulfate. The concentrations of these salts within theimmersion bath can be increased to 2% before the kinetics of reductionand aggregation overwhelm the kinetics of polymer adsorption and mixingand cause significant aggregation/clumping of the metal. The preferredmetal salt is silver (I) nitrate and is present in a concentration offrom about 0.01% to about 10%, more preferably from about 0.1% to about5.0%, and most preferably about 1.0% within the immersion bath.

The preferred reducing agents are sodium borohydride (NaBH₄), sodiumhydrosulfite, and trisodium citrate (Na₃C₆H₅O₇), although any standardreducing agent associated with the above-listed metal salts may beutilized. The former is a stronger reducing agent that reacts with themetal completely within seconds of mixing. An undesirable byproduct ofthis reaction is hydrogen gas that causes significant foaming whenmixed. The latter two do not have this effect, but are milder reducingagents and require heating to near boiling to cause the reaction toproceed.

The polymeric binder may be selected from certain resins andthermoplastics, such as melamine resins and polyvinylchloride-containing polymers. Of particular interest, and thus thepreferred polymeric binders for this process are melamine-formaldehyderesins (such as a resin available from BFGoodrich under the tradenameAerotex®), polyvinyl chloride/vinyl copolymers (such as a copolymer alsoavailable from BFGoodrich under the tradename Vycar® 460×49), andPVC/acrylic resins available from BFGoodrich. It has been found thatupon exposure to an ammonium sulfate catalyst and curing at 350° C. for2 minutes, the melamine provides durable finish on either a fiber or afabric of at least 30 washes. The copolymer requires no catalyst andperforms similarly to the melamine in wash durability when cured for thesame time and at the same temperature. (Table 1 lists the ICP readingfor silver as a function of home washes using Aerotex® M3 and BFG Vycar®in a pad.)

The solution described above can be applied to fabric or yarn in anumber of ways. Included in this list, which is by no means exhaustive,are pad coating, screen coating, spraying, and kiss-coating(particularly for yarn applications). The preferred coating and methodare discussed in greater depth below.

Metal-Ion Containing Coatings

The preferred procedures utilizing metal-ion containing compoundsinclude any of the following, depending on the desired characteristicsof the final product. One alternative utilizes the silver-ion compoundnoted above, such as either ALPHASAN®, ZEOMIC®, or IONPURE® as preferredcompounds (although any similar types of compounds which provide silverions may also be utilized), exhausted on the target fabric or filmsurface and then overcoated with a binder resin. Alternatively, themetal-ion containing compound may be admixed with a binder within a dyebath, into which the target fabric or fiber is then immersed at elevatedtemperatures (i.e., above about 50° C.).

Such a procedure was developed through an initial attempt atunderstanding the ability of such metal-ion containing compounds toattach to a fabric surface. Thus, a sample of ALPHASAN® was firstexhausted from a dye bath on to a target polyester fabric surface. Thetreated fabric exhibited excellent log kill rate characteristics;however, upon washing in a standard laundry method (AATCC Test Method130-1981, for instance), the antimicrobial activity was drasticallyreduced. Such promising initial results led to the inventivewash-durable antimicrobial treatment wherein the desired metal-ioncontaining compound would be admixed or overcoated with a binder resinon the target fabric surface. The binder resin should exhibit little orno water solubility (substantially water-insoluble), and must readilyadhere to either the fabric surface or to the metal-ion containingcompound itself. Such a binder resin can thus be selected from the groupconsisting of nonionic permanent press binders (i.e., cross-linkedadhesion promotion compounds, including, without limitation,cross-linked imidazolidinones, available from Sequa under the tradenamePermafresh®) or slightly anionic binders (including, without limitation,acrylics, such as Rhoplex® TR3082 from Rohm & Haas). Other nonionics andslightly anionics may be utilized as long as they provide the desiredadhesion characteristics. Such potential compounds include melamineformaldehyde, melamine urea, ethoxylated polyesters, such as Lubril QCX™available from Rhodia, and the like. The initial exhaustion of ALPHASAN®is thus preferably followed by a thin coating of binder resin to providethe desired wash durability characteristics for the metal-based particletreatment. The antimicrobial characteristics of the treated fabricremained very effective for the fabric even after as many as tenstandard laundering procedures. Also possible, though less effective ascompared to the aforementioned binder resin overcoat, but still anacceptable method of providing a wash-durable antimicrobialmetal-treated fabric surface, is the application of a metal-ioncontaining compound/binder resin from a dye bath mixture. The exhaustionof such a combination is less efficacious from an antimicrobial activitystandpoint than the overcoat procedure, but, again, still provides awash-durable treatment with acceptable antimicrobial benefits. Inactuality, this mixture of compound/resin may be applied throughspraying, dipping, padding, and the like.

Another preferred alternative concerns the treating of individualfibers. Such an alternative has proven very effective, most particularlyin a package dyeing method. In such a procedure, a dye bath comprisingthe desired metal-ion containing compounds and binder agents is pumpedthrough a tightly wound spool of yarn (or fiber). This is generally arather difficult process to perform effectively since the particle sizesof the constituent dye bath solids might interfere with the requisitepump pressure to force the dye bath liquor through the entire “package”of yarn. Furthermore, such a dyeing method must produce a uniformtreatment of all the portions of the target yarn throughout the“package”; particle size and thoroughness of mixing are thus of vitalimportance to impart of even treatment over the entire yarn.Surprisingly, this procedure works very well for imparting awash-durable metal treatment on the yarn surface. Upon treatment oftarget yarns, such yarns can then be woven, knit, or incorporated withina non-woven fabric structure to form a textile. The textile exhibitssimilar colorations, log kill rates, and the like, at discrete locationsof the textile. Without intending to be bound to any specific theory, itis believed that the binding agent appears to affix itself over themetal-ion containing compounds adhered to the yarn surface, or that thebinding agent adheres to the yarn surface, to which the metal-ioncontaining compound then affixes itself (and to which binding agent mayalso affix). As such, and again, very surprisingly, the desiredmetal-ion containing compounds were small enough to be forced throughthe yarn “package” in order to treat the entire target yarn.

In such an alternative method, the high pressure procedure necessary forproviding the antimicrobial solid application on the surface of thetarget yarns must be sufficient to permit penetration of the solidcompounds into the actual yarn structure. A high temperature may bedesired to permit “opening” of the fiber structure to facilitate suchsolids introduction within a solid yarn. In general, the high pressureconditions must be from about 0.1 and 100 pounds per square inch with anexposure time of from about 5 seconds to about 5 hours at a temperaturein the range from about 25° to about 325° C. Such conditions are mostreadily provided within a jet dye, closed vessel system, and appears towork most readily for package dyed yarns. The type of fiber isconsequential only to the extent that certain temperatures permit easierpenetration within certain fibers. Thus, natural fibers (such as cotton)require relatively low temperatures to “open” of the cellulosicstructure; nylon requires a much higher temperature (to exceed its glasstransition temperature, typically) to provide the most effectiveantimicrobial characteristics. For the most part, the high pressureactually appears to force the solid particles into the yarns;surprisingly, such solid-solid interaction works to retain a substantialamount of the solid antimicrobial, even after washing. Preferably,however, a binder agent is added to aid in solid particle retentionsince such solid particles will most likely exhibit a desire to becomedetached from the yarn over time.

Another alternative utilizes a metal oxide treatment on a fabric or filmsurface, such as, preferably, zinc oxide, coated with a hydrophobicbinding agent mixed with a synergistic amount of a polymeric hydrophilicmaterial, applied to a fabric or film surface, primarily to provide awash-durable odor-reducing finish on the target fabric. Generally, thepresence of such a wash-durable hydrophobic binding agent is possibleonly on a hydrophobic fabric surface. However, hydrophobic fabric doesnot wick moisture and thus is very uncomfortable to wear (if utilized asapparel fabric) as compared to a hydrophilic moisture-wicking fabric.Also, such a hydrophobic binding agent overcoat for the metal oxideodor-reducing material would detrimentally mask the metal oxide surfaceand retard the odor neutralizing action of the effective compound,particularly when present on and/or in a wet fabric. However, in orderto provide a wash-durable metal oxide odor-reducing finish to a textileor fabric, seemingly there is a need to provide a complete hydrophobicbinding agent over the metal oxide. When such a “required” excess ofhydrophobic agent binder is present, again, the metal oxide (i.e., zincoxide) would most likely be encapsulated and thus will not contact thetargeted odor-producing compounds. A reduction in such hydrophobicbinding agent results in a lack of sufficient adhesion between the metaloxide particles and the target fabric to provide a wash-durable andwear-durable finish. It was found, surprisingly, that the necessarycomfort (due to wicking of moisture) and simultaneous retention ofsufficient adhesion are provided through the addition of a hydrophilicagent to the zinc oxide/binding agent formulation. With such anaddition, a durable, moisture-wicking, and odor-reducing textilefinish/coating is provided. Of great and surprising interest is theapparent synergistic interaction between the zinc oxide, binding agentand hydrophilic agent. The hydrophilic agent not only providesmoisture-wicking comfort to the target fabric, but also facilitates theinteraction of odor compounds in human perspiration with the preferredzinc oxide to allow efficient odor neutralization. In general the weightratio of zinc oxide to resin binder is in the range of 100:1 to 1:100 tobe effective. The ratio between 1:2 and 2:1 is preferred. One suitablewetting agent for this application may possess both hydrophilic andhydrophobic moieties within its structure. In such an instance, thespecific hydrophilic moiety must be present in an amount sufficient topermit any moisture spread on the treated fabric surface. The finishalso requires sufficient amounts of a hydrophobic moiety within itsstructure to make it water soluble. As a result, the finish will not beeasily washed off in repeated washing cycles. Examples of such preferredwetting agents are sulfonated polyesters, ethylene oxide-propylene oxidecopolymers, and ethoxylated polyesters. The preferred metal oxide iszinc oxide with fine particle size and high surface area. Fine particlesize allows uniform distribution in an application medium and rendersthe treatment substantially transparent. Large particle zinc oxide tendsto give a white background shade to a textile and therefore affects theappearance of the product. Particle sizes for this application should bepreferably below 3 micrometers, most preferably, less than 1 micrometer.Zinc oxide high specific surface area is also preferred for thisapplication. Preferred specific surface area of zinc oxide for thisapplication is 10 m²/g or more.

The preferred embodiments of these alternatives fabric treatments arediscussed in greater detail below.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Examples of particularly preferred compounds within the scope of thepresent invention are set forth below. None of the following inventivefabrics exhibited any electrical conductivity.

A) Silver-Particle Yarn and Fabric Treatments

The dispersions used in the durability and log kill study for theresultant articles with silver-particle treatments contained thefollowing concentrations (all % are per weight of solution): 1% AgNO₃,0.5% NaBH₄, 5% binder resin, 3% hydroxyethylcellulose thickener, and90.5% water. The print pattern used was a 12 dpi dot pattern with eachdot having ˜0.5 mm diameter circular shape.

Three sets of samples were tested at three different numbers of washes.The three sets were: a) untreated 100% polyester multifilament fabric,b) the same type of fabric treated with ust the desired binder resin,and c) the same type of fabric treated with the above-describedsilver-particle dispersion. Each sample was tested for 0, 15 and 30washes. To minimize the potential biocidal activity of the detergent,the 15 and 30 wash samples were run through two additional rinse cyclesbefore analysis. In the pertinent Tables which follow, the log killresults were performed with a) an initial Staphylococcus aureusconcentration of 3.8×10⁶ CFU/mL and b) a Klebsiella pneumoniae inocculuminitial concentration of about 18,000,000 CFU/mL.

The following three treatments were performed and shown to be create ahighly washfast metal particle finish:

1) Pad Coating

The fabric article (100% polyester fabric) was dipped into a silverparticle/polymeric dispersion comprising about 1 part of silver colloidsolution and about 5 parts of a binder resin. Particular resins testedwere Aerotex(g) M3, Vycar® 460×49, and a PVC/Acrylic resin (all resinsavailable from BFGoodrich). The immersed fabric was then removed and runthrough a pad roll. The fabric was then heated to 350° C. for 2 minutes.The resulting fabric was then first analyzed for particle countremaining on the fabric surface after treatment by ICP spectroscopy,both initially and after a number of washes utilizing the standardlaundering procedure of AATCC Test Method 130-1981. The results arepresented in tabular form below:

TABLE 1 Particle Count on Fabrics Pad Coated with Silver ParticleDispersions # of ICP for Silver (ppm) ICP for Silver (ppm) WashesPVC/Acrylic Binder With Aerotex ® M3 Binder  1 5210 7074 10 3993 6250 203555 6149 30 2841 4965Thus, the retention of the metal finish was excellent for both binders(77% after 10 washes, 68% after 20, 55% after 30 for the PVC/Acrylicbinder; 88% after 10 washes, 87% after 20, and 70% after 30). It shouldbe noted that these measurements are subject to the variability withinthe measuring instrument as well; although they are consideredrelatively and should not deviate in any significant amount from thetabulated results, variations in results may occur. Furthermore, thetreated fabrics were also tested for electrical conductivity through themethod noted above (AATCC Test Method 76-1978); the noise of themeasuring instrument exceeded any signal of the resistance measuringinstrument, thus, the resistance is so high for the fabric that noappreciable conductivity was exhibited by all of the tested samples.2) Yarn Application

In this method, the metal particle dispersion was applied utilizing akiss-coater, which consists of a roll which constantly rotates in a bathof the metal dispersion. The roll transferred the solution to the topside of the roller, where an end of yam passed against the roller andinto an oven where it was cured at 350° C. for 2 minutes then taken uponto a bobbin for further processing. The metal particle coated yam wasmeasured to be electrically non-conductive (by the spaced electrodemethod noted above) and typically included from about 20 to 30% byweight of the metal-particle dispersion. The silver-coated yam was thenknit or woven into a fabric with non-treated yams at a ratio of 1treated yam to every 15 untreated yams. The treated yams were visible ononly one side of the treated fabric and the resultant fabric exhibitedexcellent sustained antimicrobial performance. Table 3 shows ICP resultsfor silver as a function of washes for a “sock” knit from 70 deniertreated yam and 500 denier untreated yam.

TABLE 2 Durability of Silver-Particle Coated Yarns Woven into FabricsICP for Silver (ppm) # of Home With Aerotex ® M3 Washes Binder  0 379810 3709 20 3297 30 32863) Screen Printing

In a screen printing application, the dispersion described above wasthickened and pressed through a printing screen onto one side of afabric in a finishing step. The preferred thickening agent for thisembodiment is Aqualon® Natrosol 99-250 HHR (in a concentration range of1-10% by weight of solution) with the preferred concentration being 3%(which provides a desired intrinsic viscosity of from about 100,000 toabout 400,000, preferably 200,000, centipoise at standard temperatureand pressure). The viscosity of the metal particle/polyer dispersion mayalso be adjusted with the utilization of sufficient amounts ofhydroxyethylcellulose; however, mixtures of HEC and the Aqualon®thickeners may prove sufficient to provide a resultant, preferredviscosity of 200,000 cps. Although preferred thickeners for screenprinting have been found, one of ordinary skill in this art wouldappreciate that any number of acceptable thickeners may be utilized,either alone, or in combination, to provide the desired and/or necessityviscosity level in order to perform such a screen printing procedure.The thickened metal-particle containing dispersion was applied to thetarget fabric by squeezing it through a patterned rotary screen. The“coated” fabric was then cured at 350° F. for at least 2 minutes toproduce a coating that washfast through at least 30 washes. Table 4provides this durability data:

TABLE 3 Durability of Screen Printing on Fabric with Silver-ParticleDispersions # of Home ICP for Silver (ppm) Washes With PVC/AcrylicBinder  0 312 10 266 20 135 30 109

The treated fabric was then analyzed for its ability to provideantimicrobial effectiveness against Staphylococcus aureus and Klebsiellapneumoniae. The results were as follows:

TABLE 4 Staphylococcus aureus Effectiveness # Washes Control BinderFabric from TABLE 3  0 0.35 0.83 5.56 15 1.00 1.06 4.08 30 0.07 1.205.54

TABLE 5 Klebsiella pneumoniae Effectiveness # Washes Control BinderFabric from TABLE 3  0 1.93 2.28 3.94 15 2.73 2.79 5.33 30 2.04 2.665.33

The durable treatment not only retained its integrity over the targetfabric surface, but also continued to provide an effective antimicrobialtreatment as well.

B) Silver Ion Exchange, Silver Zeolite, and Zinc Oxide Fabric TreatmentsAs noted above, treatments of specific metal-ion containing compoundshave proven to be wash-durable on certain yam and fabric surfaces aswell. These include the following, preferably with either the ALPHASAN®silver-based compounds or with zinc oxide. The following preferredembodiments exhibited resistivity measurements well in excess of 1×10⁹ohms per square inch of fabric in accordance with AATCC Test Method76-1978.1) Exhaustion of Compound Followed with Binder Resin Overcoat

a) Acrylic Binder Resin—A dispersion of ALPHASAN® (silver-based ionexchange compound available from Milliken & Company) was first producedthrough the mixing of about 30% by weight of the silver-based compound,about 23.0% by weight of a mixture of anionic surfactants, Tamol® SN,available from Rohm & Haas, and Synfac® 8337, available from Milliken &Company, and the remainder water. This dispersion was then appliedthrough exhaustion within a dye bath to four fabric samples (all of 100%polyester construction; with 51 picks by 52 ends; 300 deniermultifilament yam). Two were dyed at a temperature of about 280° F.; theothers at a temperature of about 265° F. The exhaustion level of theactive ALPHASAN® compounds on the target fabrics was about 1.0% owf. Thefabrics were then coated with an acrylic binder material, Rhoplex®TR3082, in an amount of about 2.5% owf. The coated fabrics were thenheat-set at 380° F. The log kill rate for unwashed fabrics for S. aureuswas measured to be 4.9; for K. pneumoniae, 2.54. The results aftermultiple washings are tabulated below:

TABLE 6 Log Kill Rates After Multiple Washings With Acrylic OvercoatNumber of Washes Log Kill Rate for S. aureus Log Kill Rate for K.pneumoniae 1 4.59 2.28 5 4.15 2.20 10  3.13 1.97It is important to note, and as is well appreciated and understood byone of ordinary in the art, that variations in log kill ratemeasurements are prevalent, though, reliable, due to inherentdifficulties in both biological testing and in the ability to establishcompletely controlled bacterium counts on such surfaces. These resultsthus show very favorable antimicrobial performance and thus excellentwash durability on the fabric surface.

b) Permanent Press Binder Resin—The same type of ALPHASAN® dispersionand exhaustion procedure was followed as above. The overcoat, however,was Permafresh®, available from Sequa. Again, about 2.5% owf of thisovercoat resin was applied over the ALPHASAN®-treated fabrics. Alsoadded within the dye bath was a butyl benzoate carrier in an amount ofabout 2.5% owf. The log kill results for this sample were as follows:

TABLE 7 Log Kill Rates After Multiple Washings With Permanent PressOvercoat Number of Washes Log Kill Rate for S. aureus Log Kill Rate forK. pneumoniae 0 3.21 5.32 1 4.11 3.89 5 2.98 3.03 10  3.94 4.23Excellent durability results were thus obtained with such a system.

c) PD-92 Binder Resin—The same type of ALPHASAN® dispersion andexhaustion procedure was followed as above. The overcoat, however, wasPD-92 available from Milliken & Company. Again, about 2.5% owf of thisovercoat resin was applied over the ALPHASAN®-treated fabrics. Alsoadded within the dye bath was a butyl benzoate carrier in an amount ofabout 2.5% owf. The log kill results for this sample were as follows:

TABLE 8 Log Kill Rates After Multiple Washings With PD-92 OvercoatNumber of Washes Log Kill Rate for S. aureus Log Kill Rate for K.pneumoniae 0 3.30 3.36 1 3.15 2.72 5 3.18 2.26 10  3.03 1.78Excellent durability results were thus obtained with such a system aswell.

d) Effect of Increased amount of ALPHASAN® on Wash Durability—The samefabric treatments (with Permafresh® binder resin) as above wereperformed with the amount of ALPHASAN® increased to a 4% owf activeaddition to the target fabric surface (about 13.3% owf of thedispersion). The same padding on of the permanent press binder wasfollowed as above. The log kill results for K. pneumoniae are asfollows:

TABLE 9 Log Kill Rates With High Add-On of Silver-Based Compound Numberof Washes Log Kill Rate for K. pneumoniae 0 5.6 5 5.7 10  4.4Again, excellent durability was obtained.

e) Effect of Increased amount of Permanent Press Binder Resin on WashDurability—The same fabric treatments (with Permafresh® binder resin) asabove were performed with the padded on amount of binder resin increasedto a 7.5% owf addition to the target fabric surface. The log killresults for K. pneumoniae are as follows:

TABLE 10 Log Kill Rates With High Add-On of Permanent Press Binder ResinNumber of Washes Log Kill Rate for K. pneumoniae 0 5.7 5 4.0 10  3.9Again, excellent wash durability results were obtained.2) Exhaustion of Compound with a Binder Resin

A dispersion of ALPHASAN® (silver-based ion exchange compound availablefrom Milliken & Company) was first produced through the mixing of about30% by weight of the silver-based compound, about 23.0% by weight of ananionic surfactant mixture of Tamol® and Synfact 8337 surfactant, andthe remainder water. This dispersion was then applied through exhaustionwithin a dye bath which included an acrylic binder (Rhoplex® TR3082)which was present within the dye bath in a concentration of about 2.5%owf. A 100% polyester fabric (same as above) was then placed within thedye bath which was then heated to a temperature of about 280° F. Theexhaustion level of the active ALPHASAN® compounds on the target fabricswas about 1.0% owf. The fabrics were then heat-set at 380° F. The logkill rate for unwashed fabrics for S. aureus was measured to be 2.35;for K. pneumoniae, 5.38. The results after multiple washings aretabulated below:

TABLE 11 Log Kill Rates After Multiple Washings With Acrylic ResinNumber of Washes Log Kill Rate for S. aureus Log Kill Rate for K.pneumoniae 1 1.50 2.37 5 1.17 2.37 10  1.36 2.98These results show very favorable antimicrobial performance and thusexcellent wash durability on the fabric surface, though less favorablethan for the resin overcoated fabrics.3) Exhaustion of Other Silver-Based Compounds

The same general exhaustion methods were followed as above with the samepadding on (denoted as P in the table below) and dye bath application (Din the following table) of a permanent press binder as above as well.The different silver-based compounds applied were AmpZ200 (a TiO2/silvermetal product available from DuPont), and ZEOMIC® AJ80H. The add-onweights of these were the same 1.0% owf treatment as for the ALPHASAN®noted above. The durability results for these compounds were as followsfor K. pneumoniae log kill rates:

TABLE 12 Log Kill Rates With Other Silver-Based Compounds NumberCompound of Washes Log Kill Rate for K. pneumoniae AmpZ200 (P) 0 2.76AmpZ200 (P) 10 1.82 AmpZ200 (D) 0 2.06 AmpZ200 (D) 10 1.36 ZEOMIC ®AJ80H (P) 0 5.31 ZEOMIC ® AJ80H (P) 10 1.64 ZEOMIC ® AJ80H (D) 0 4.31ZEOMIC ® AJ80H (D) 10 1.92These are excellent durability results, although not as good as for theALPHASAN® treatments.4) Package Dyeing Method

Again, as with al of the other inventive fabrics and yams, the measuredresistivity of the following yams and fabrics exceeded 1×10⁹ ohms persquare inch.

EXAMPLE 1

Several spools of 150 denier polyester multifilament yarn were placedwithin a sealed dye bath. The dye bath liquor contained 1.0% owf ofactive ALPHASAN®, 0.5% by weight of nonionic leveler 528 (butylbenzoate, available from Milliken & Company), and the balance water.After sealing of the chamber, the pump was activated at a pressure of 60psi at a temperature of about 280° F. The pump remained activated forabout 60 minutes. The resultant spools of yam were then utilized in aknitting operation to produce a sock. Three different discrete areas ofthe sock were tested for log kill rates for K. pneumoniae afterdifferent numbers of launderings. The colorations of the sock remainedvirtually the same after such repeated launderings. The log kill resultsare tabulated below:

TABLE 13 Log Kill Rates On The Knit Fabrics (Binder-Free) Number ofWashes Log Kill Rate for K. pneumoniae 0 4.43 5 4.13The knit fabric thus retained a substantial amount of its ALPHASAN®finish applied during the package dyeing process for an extremely longduration.

EXAMPLE 2

Several spools of 150 denier multifilament polyester yam were placedwithin a sealed dye bath. The dye bath liquor contained 1.0% owf ofactive ALPHASAN®, 0.5% owf nonionic leveler 528, 2.0% owf of Rhoplex®TR3082 (an acrylic-based slightly anionic binding agent), and thebalance water. After sealing of the chamber, the pump was activated at apressure of 60 psi at a temperature of about 280° F. The pump remainedactivated for about 60 minutes. The resultant spools of yam were thenutilized in a knitting operation to produce a sock. Three differentdiscrete areas of the sock were tested for log kill rates for K.pneumoniae after different numbers of launderings. The colorations ofthe sock remained virtually the same after such repeated launderings.The log kill results are tabulated below:

TABLE 14 Log Kill Rates On The Knit Fabrics (With Acrylic Binder) Numberof Washes Log Kill Rate for K. pneumoniae 0 4.43 5 4.20 10  4.03The knit fabric thus retained a substantial amount of its ALPHASAN®finish applied during the package dyeing process for an extremely longduration.

EXAMPLE 3

Several spools of 150 denier multifilament polyester yarn were placedwithin a sealed dye bath. The dye bath liquor contained 1.0% owf ofactive ALPHASAN®, 0.5% owf of nonionic leveler 528, and the balancewater. After sealing of the chamber, the pump was activated at apressure of 60 psi at a temperature of about 280° F. The pump remainedactivated for about 60 minutes. The resultant spools of yarn were thenutilized in a knitting operation to produce a sock. A permanent pressbinding agent (2.0% owf of Permafresh®, available from Sequa) was thenpadded on the entire sock. After drying, three different discrete areasof the sock were tested for log kill rates for K. pneumoniae afterdifferent numbers of launderings. The colorations of the sock remainedvirtually the same after such repeated launderings. The log kill resultsare tabulated below:

TABLE 15 Log Kill Rates On The Knit Fabrics (With Permanent PressBinder) Number of Washes Log Kill Rate for K. pneumoniae 0 4.43 5 4.4210  3.85The knit fabric thus retained a substantial amount of its ALPHASAN®finish applied during the package dyeing process for an extremely longduration.Metal Oxide Odor Reduction Fabric Treatments

A dispersion having the following components was mixed thoroughly:

COMPOSITION Component Amount (in grams) Zinc oxide powder (Aldrich, <1micron) 2.0 grams Rhoplex ® E-32NP (acrylic resin binder) 8.0 gramsMillitex ® PD-92 (wetting agent) 2.0 grams Ultratex ® MES (fabricsoftener) 0.5 grams water 90 gramsOne swatch of dyed knit polyester fabric was impregnated with the mixedsolution and dried at 350° F. for 3 min to obtain a treated fabric. Thetreated fabric exhibited no noticeable color or flexibility change.Several drops of a dilute aqueous isovaleric acid solution (1 drop ofacid in 50 grams of water), to simulate unpleasant foot odor, was thenapplied to the unwashed fabric. The solution quickly wicked into thefabric and the unpleasant odor quickly disappeared. The treated fabricwas then laundered in accordance with the AATCC Test Method 130-1981 for10 cycles; the same wicking and odor removal was exhibited by the zincoxide treated fabric. Thus, the zinc oxide treatment remained intact onthe fabric surface. Furthermore, the sample was tested for electricalconductivity by measuring resistance over the entire fabric. The fabricsample exhibited 10¹³ ohms/square inch of fabric; thus, effectively noconductivity existed.

The sample was then washed in accordance with AATCC Test Method 130-1981and then analyzed for odor reduction and antimicrobial activity inaccordance with 24 hour inoculation exposure of Klebsiella pneumoniaeunder AATCC Test Method 100-1983. The results were as follows:

TABLE 16 # of Washes Log Kill Reduction Odor Neutralization?  1 3.1 Yes10 3.6 Yes 25 ~3.0 Yes

Furthermore, X-ray fluorescence was performed on the above sample toindicate the amount of zinc retained on the fabric surface as wellthrough the peak size in relation to the signal emitted by zinc on thesubstrate surface. The results were as follows:

TABLE 17 Number of washes Zinc X-ray counts  0 162,644  2 113,133 10 87,471 20  49,801Thus, excellent wash durability was exhibited even after twenty washessince about 30% was retained from the initial zinc count.Lightfastness of Certain Samples

The samples tested in TABLE 6, above, as well as other fabrics andcomparative samples were analyzed for the lightfastness of the colorexhibited by the treated fabrics after topical application of thedesired metal-based finish. Such analysis involved testing in accordancewith The Engineering Society for Advancing Mobility Land Sea Air andSpace Textile Test method SAE J-1885, “(R) Accelerated Exposure ofAutomotive Interior Trim Components Using a Controlled Iradiance WaterCooled Xenon-Arc Apparatus.” Colorlightfastness is generally calculatedby the following equation:ΔE*=((L _(initial) *−L _(exposed)*)²+(a _(initial) *−a_(exposed)*)²+(b_(initial) *−b _(exposed))²)^(1/2)wherein ΔE* represents the difference in color between the fabric uponinitial latex coating and the fabric after the above-noted degree ofultra violet exposure. L*, a*, and b* are the color coordinates; whereinL* is a measure of the lightness and darkness of the colored fabric; a*is a measure of the redness or greenness of the colored fabric; and b*is a measure of the yellowness or blueness of the colored fabric. A lowΔE* shows excellent lightfastness for the tested fabric; a ΔE* greaterthan about 5.0 is unacceptable and shows a yellowing tendency for thetreated fabric. As noted above, the ALPHASAN®-treated polyester samplefrom TABLE 6 was subjected to a Xenon Arc Lamp Test at 225 kJ/m² forboth 20 and 40 hours to analyze the yellowing characteristics of thetreated fabric. At 20 hours, the fabric exhibited a ΔE* of about 1.95;at 40 hours, a ΔE* of about 3.38. Thus, the treated fabric exhibitedexcellent lightfastness properties.

Further samples of 65%/35% polyester/cotton blend shirts were alsotested for such lightfastness results after receiving ALPHASAN®treatments from dryer donor sheets comprising 0, 9%, and 20% (made inaccordance with the method discussed above) of the silver-based ionexchange compound. The results were tabulated as follows:

TABLE 18 Amount of ALPHASAN ® ΔE* at 20 hours ΔE* at 20 hours 0 0.480.72 9 1.03 1.23 20  1.34 1.82Clearly and surprisingly, the silver treated fabrics exhibitedacceptable lightfastness characteristics.

There are, of course, many alternative embodiments and modifications ofthe present invention which are intended to be included within thespirit and scope of the following claims.

1. A treated substrate comprising a finish comprising metal compoundsselected from the group consisting of silver particle-containingcompounds, silver ion-containing compounds, silver ion-generatingcompounds, and any combinations thereof, and a substrate selected fromthe group consisting of a yarn, a fabric comprised of individual fibers,and a film; wherein said finish is adhered to at least one portion ofthe surface of said substrate; wherein said at least one portion of saidtreated substrate retains at least about 50% of said adhered to finishafter 10 washes as performed in accordance with the wash procedure ofAATCC Test Method 130-1981; wherein said finish contains a binder agentand 0.1 to 40 weight percent of the metal compound, or wherein the atleast one portion of said treated substrate is covered with a binderformulation; wherein said treated substrate is electricallynon-conductive; and wherein said finish exhibits antimicrobialproperties.
 2. The treated substrate of claim 1, wherein said substrateis an individual yarn.
 3. The treated substrate of claim 1, wherein saidsubstrate is a textile fabric.
 4. The treated substrate of claim 1,wherein said substrate is a film.
 5. A treated substrate of claim 1,exhibiting a log kill rate for Staphylococcus aureus of at least 1.5 anda log kill rate for Klebssiella pneumoniae of at least 1.5, both astested in accordance with AATCC Test Method 100-1993 for 24 hourexposure, after at least 10 washes, said washes performed in accordancewith the wash procedure as part of AATCC Test Method 130-1981.
 6. Thetreated substrate of claim 1, wherein the metal compound is a silverion-containing compound.
 7. The treated substrate of claim 1, whereinthe metal compound is present in an amount of between 0.01 to 1.0 ouncesper square yard.
 8. The treated substrate of claim 1, wherein thesubstrate is a fabric comprised of cotton fibers, wool fibers, ramiefibers, hemp fibers, linen fibers, polyolefin fibers, polyester fibers,polyamide fibers, polyaramid fibers, acetate fibers, rayon fibers,acrylic fibers, or blends thereof.
 9. The treated substrate of claim 8,wherein the substrate is a fabric comprised of polyester fiber.
 10. Thetreated substrate of claim 1, wherein the binder is selected from thegroup consisting of cross-linked imidazolidinones, acrylic binders,melamine resins, polyvinyl chloride-containing polymers, ethoxylatedpolyesters, or blends thereof.
 11. The treated substrate of claim 1,wherein the binder is anionic or nonionic, and wherein the binder, afterprocessing and application to the substrate: (a) is not readily solublein water, (b) is not susceptible to attack by standard launderingadditives selected from the group consisting of detergents, solvents,bleaches, and mixtures thereof, and (c) is not susceptible todegradation due to exposure to high temperatures associated withstandard laundry drying temperatures.
 12. The treated substrate of claim6, wherein the silver ion-containing compound is silver zirconiumphosphate.